Salma Dhifaoui, A. Azaid, M. Bourass, Laila Ben Haj Hassen, H. Nasri, M. Bouachrine
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引用次数: 1
摘要
本文通过密度泛函理论(DFT)计算、自然键轨道(NBO)分析和Hirschfeld表面分析对双(4-氰吡啶)[(中四基(4-甲氧基苯基卟啉)]铁(III)三氟甲烷磺酸氯苯单溶剂配合物(I)进行了研究,并利用各种量子化学方法对铁卟啉衍生物(I)的结构进行了优化:HF、B3PW91、BPV86和B3LYP分别具有3-21、6-31 G (d, p)和6-311 G (d, p)三个碱基。(I)的理论结构参数与x射线分子结构得到的参数非常接近。从优化后的结构出发,计算并讨论了HOMO-LUMO能、偶极矩、分子静电势、Mulliken电负性、化学硬度和电子势等参数。另一方面,得到了(I)的吸收特性,并与实验紫外可见光谱得到的吸收特性进行了比较。用局部柔软度、亲电性、电负性、硬度、HOMO-LUMO间隙等描述符计算了[FeIII (TMPP) (4-CNpy)2] +离子配合物的反应性,并讨论了(I)晶体填充物的Hirschfeld数据。
DFT Studies on Molecular Structure, Absorption properties, NBO Analysis, and Hirshfeld Surface Analysis of Iron(III) Porphyrin Complex
In this work, the Density Functional Theory (DFT) calculations, the Natural Bond Orbital (NBO) analysis, and the Hirschfeld surface analysis were carried out on the bis(4-cyanopyridine) [(meso-tetrakis(4-metoxyphenylporphyrinato)] iron (III) trifluoro-methane sulfonate chlorobenzene mono-solvate complex (I). The structure of the ferric porphyrin derivative (I) was optimized by using various quantum chemical methods: HF, B3PW91, BPV86, and B3LYP with three bases set 3-21, 6-31 G (d, p), and 6-311 G (d, p). The theoretical structural parameters of (I) are very close to those obtained by X-ray molecular structure. From the optimized structure, several parameters such as the HOMO-LUMO energies, the dipole moments, the molecular electrostatic potentials, the Mulliken electronegativity, the chemical hardness, and the electronic potential were calculated and discussed. On the other hand, the absorption properties of (I) were obtained and compared with those obtained with the experimental UV-visible spectrum. The reactivity of our [FeIII (TMPP) (4-CNpy)2] + ion complex using various descriptors such as local softness, electrophilicity, electronegativity, hardness, HOMO-LUMO gap, were calculated and the Hirschfeld data of the crystal packing of (I) were discussed.
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